CN1882507A - System and method for removing arsenite and arsenate from water - Google Patents

System and method for removing arsenite and arsenate from water Download PDF

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Publication number
CN1882507A
CN1882507A CNA2004800342747A CN200480034274A CN1882507A CN 1882507 A CN1882507 A CN 1882507A CN A2004800342747 A CNA2004800342747 A CN A2004800342747A CN 200480034274 A CN200480034274 A CN 200480034274A CN 1882507 A CN1882507 A CN 1882507A
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liquid
water
reaction
arsenic
cupric oxide
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K·J·雷迪
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University of Wyoming
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University of Wyoming
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C02F1/003—Processes for the treatment of water whereby the filtration technique is of importance using household-type filters for producing potable water, e.g. pitchers, bottles, faucet mounted devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0233—Compounds of Cu, Ag, Au
    • B01J20/0237—Compounds of Cu
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/427—Treatment of water, waste water, or sewage by ion-exchange using mixed beds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/103—Arsenic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2307/00—Location of water treatment or water treatment device
    • C02F2307/06—Mounted on or being part of a faucet, shower handle or showerhead
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00—Liquid purification or separation
    • Y10S210/902—Materials removed
    • Y10S210/911—Cumulative poison
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00—Liquid purification or separation
    • Y10S210/902—Materials removed
    • Y10S210/911—Cumulative poison
    • Y10S210/912—Heavy metal

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Water Treatment By Sorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Removal Of Specific Substances (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

A method for removing arsenite and arsenate from water is provided. The method comprises reacting the water with cupric oxide (CuO) particles for a predetermined time and filtering the reacted water. A system for removing arsenite and arsenate from liquids is also provided.

Description

Be used for removing the system and method for arsenite and arsenate from water
The application is the continuation of the temporary patent application series number 60/504,329 undetermined that is entitled as " system and method that is used for removing from water arsenite and arsenate " of submission on September 19th, 2003.
Technical field
Relate generally to of the present invention is used for removing from water the system and method for arsenite and arsenate, more specifically, the present invention relates to a kind of like this system and method that is used for removing from water arsenite and arsenate, it comprises water and cupric oxide (CuO) the particle reaction preset time that makes arsenic contamination.
Background technology
Arsenic is the material that occurring in nature exists, and it exists with multiple combined form in the earth.The arsenic contamination of tap water has been reported in many in the world places.USEPA (EPA) represents that the arsenic in the tap water can make the people carcinogenic, and under the concentration that allows at present in the water amount of arsenic may equal by the caused amount of smoking.
Arsenic is that 5A family is nonmetal, and more common valency is-3,0 ,+3 and+5.Arsenite (As + 3) and arsenate (As + 5) be prevailing existence form in tap water and the waste water streams.In the area of some arsenic influence, be very expensive by alternative existing drinking water source, the drinking water source of safety and utilization easily.In order to satisfy people's tap water, irrigation water, domestic animal and Wildlife water and hydrobiological high pollution thing level (MCL), must remove arsenic to reach safety margin.In fact, in these cases, the removal of arsenic may be more suitable water supply scheme.
Therefore, water supply person needs a kind of safety method of economy to come to remove arsenic from tap water.In addition, the resident family that from well, obtains water need low cost, safety and effectively arsenic remove the inlet point of system or use point.
There is the method for some arsenic removals in past, comprising: adsorb on activated alumina in fixed bed contactor (1); (2) make arsenic and the coordination of aqueous metal throw out in common water treatment device, the past is aluminium and iron hydroxide or oxyhydroxide; (3) by membrane technique for example reverse osmosis from water, leach metal; (4) electrodynamic method, for example electrodialysis.
Lamentedly, the method for prevailing removal arsenic is difficult to remove arsenite (As + 3).Though some technology is quite successful in the large-scale city supply, they are used for dwelling house is unpractiaca, because require big space, needs to use hazardous chemical, needs often monitoring, and big expense.In fact, each of these methods all needs the technician of high degree of skill to carry out daily operation and maintenance, and this makes them be not suitable for being used for dwelling house at inlet point and uses.
Be used for the gauged two kinds of prevailing technology of dwelling house water is reverse osmosis (RO) and activated alumina always.Activated alumina need be used the chemical of causticity, and needs very large volume for the high flow capacity that uses the present invention to reach.RO has been proved to be and has not been arsenic removal technology, because it can not reduce arsenite (As significantly + 3).
Summary of the invention
The present invention is the method for removing arsenite and arsenate from water.Described method comprises makes described water and cupric oxide (CuO) particle reaction preset time, the water of filtering reaction then.
The present invention also comprises the system that is used for removing from water arsenite and arsenate.Described system comprises by the water of arsenic contamination, is added into cupric oxide (CuO) particle in the water of pollution, is used to filter the strainer of CuO/ water.
Description of drawings
Fig. 1 is the process of arsenic is removed in explanation from the water that pollutes according to the present invention a sketch map;
Fig. 2 is the sketch map of explanation according to the filtration unit design of the present invention's formation; With
Fig. 3 is the sketch map of explanation according to the filter design of the present invention's formation.
Embodiment
The preparation of cupric oxide:
The method that proposes is used cheap solids, and removes arsenite and arsenate from water.Removing kinetics is rapidly, and method is simple, and this method does not produce deleterious byproduct.From water, the arsenic material reduced to and be lower than ten (10) micrograms per litre of EPA the requirement of people's tap water.Regulate (pH is 6.0) at pH and do not regulate under (pH is between the 7.5-8.5) and experimentize system.
When sodium hydroxide and cupric chloride reaction, form copper hydroxide.When copper hydroxide was at room temperature placed one, it was precipitated out as cupric oxide.
CuO is filtered, drying, grinding then is fine powder.The CuO of this prepared in laboratory is used to remove arsenic from water.
The preparation of standard model:
The arsenite standard model uses arsenus acid sodium salt (NaAsO 2) preparation.
Use the arsenite standard substance of 1000ppm to prepare 1ppm, 500ppb, 250ppb, the arsenite standard model of 100ppb and 10ppb.
Use arsenic acid sodium salt (Na 2AsO 4) preparation arsenate standard model.
Use the arsenate standard substance of 1000ppm to prepare 1ppm, 500ppb, 250ppb, the arsenate standard model of 100ppb and 10ppb.
Sodium sulfate salt (Na 2SO 4) be used to prepare 1,250ppm, 1,000ppm, the vitriol standard model of 250ppm and 50ppm.
Experiment
The preparation arsenic standard solution, and the standardized solution of every crowd of 50ml and 0.5 gram CuO are reacted.Erlenmeyer flask is fixed on the mechanical shaker, and the reaction preset time.After reaction, solution is filtered, and use ICP analytical reagent composition arsenic.
The result:
1. arsenite and 0.50 restrains the CuO particle reaction.
As standard model (ppb) Total arsenic concentration before reaction Total arsenic concentration after reaction Remove percentage
10 8 -0.3 100
100 87 -0.1 100
250 217 -0.3 100
500 426 -0.1 100
1000 868 -0.1 100
2. arsenate and 0.25 restrains the CuO particle reaction.
As standard model (ppb) Total arsenic concentration (ppb) before reaction Total arsenic concentration (ppb) after reaction Remove percentage
10 8 0 100
100 87 0.3 99.65
250 217 24.8 88.57
500 426 85.1 80.02
1000 868 210.7 75.80
3. the vitriol of the arsenite of 500 (500) ppb and different concns and 0.5 restrains the CuO particle reaction.
Sulfate concentration (ppm) before the reaction Sulfate concentration (ppm) after the reaction Total arsenic concentration (ppb) before the reaction Total arsenic concentration (ppb) after the reaction Remove percentage
1070 1055 540.9 1.2 99.77
1303 1293 555.8 4.1 99.26
269 260 544.9 2.7 99.50
64.2 57.9 610.4 0.1 99.98
4. arsenate and 0.5 restrains the CuO particle reaction.
Arsenate standard model (ppb) Total arsenic concentration (ppb) before the reaction Total arsenic concentration (ppb) after the reaction Remove percentage Cu2+ concentration (ppb) after the reaction
10 14 0 100 3426
100 82 1 98.78 779
250 257 0 100 325
500 428 0 100 340
1000 837 0 100 124
5. the vitriol of the arsenate of 500 (500) ppb and different concns and 0.5 restrains the CuO particle reaction.
Sulfate concentration (ppm) before the reaction Sulfate concentration (ppm) after the reaction Total arsenic concentration (ppb) before the reaction Total arsenic concentration (ppb) after the reaction Remove percentage Cu2+ concentration (ppb) after the reaction
1277.3 1268.6 430 1 99.76 206
263.6 244.6 430 0 100 10
50.3 42.7 352 0 100 10
From the water that four kinds of different logistics are collected spike (spiked) and with the arsenate (125ppb) of 0.5 gram CuO particle reaction.
Logistics Total arsenic concentration (ppb) before the reaction Total arsenic concentration (ppb) after the reaction Remove percentage Cu2+ concentration (ppb) before the reaction Cu2+ concentration (ppb) after the reaction Sulfate concentration (ppm) after the reaction
Oregon 146.3 2.9 98.00 9.1 17.5 628.0
Six Mile Drain 125.2 0 100 0.0 36.3 740.0
Casper 119.0 0 100 0.0 33.1 1439.0
Bait′s 117.8 0 100 0.0 15.3 573.0
From the water that four kinds of different logistics are collected spike and with the arsenite (150ppb) of 0.5 gram CuO particle reaction.
Logistics Total arsenic concentration (ppb) before the reaction Total arsenic concentration (ppb) after the reaction Remove percentage Cu2+ concentration (ppb) before the reaction Cu2+ concentration (ppb) after the reaction Sulfate concentration (ppm) after the reaction
Oregon 156.5 25.7 83.57 4.0 15.4 628.0
Six Mile Drain 149.6 0 100 2.9 11.9 740.0
Casper 143.6 0 100 4.4 50.2 1439.0
Bait′s 142.5 0 100 4.6 14.6 573.0
Below under the situation of not carrying out pH regulator, from natural water, remove arsenic data show, utilize the present invention can from water, remove arsenic.
Sample Arsenate (micrograms per litre) before the reaction Arsenate (micrograms per litre) after the reaction Remove percentage
B-1 133.6 0.7 99.4
B-3 141.5 0.7 99.5
B-5 136.7 1.0 99.2
B-7 139.7 0.9 99.3
Sample Arsenite (micrograms per litre) before the reaction Arsenite (micrograms per litre) after the reaction Remove percentage
B-2 124.9 1.6 98.6
B-4 117.0 1.3 98.8
B-6 119.0 5.4 95.4
B-8 121.0 0.3 99.7
In the present invention, three kinds of possible mechanism that are used under field conditions (factors) by CuO particle effective elimination arsenic material have been had been found that: 1) be in higher pH, so these particles can have the affinity of higher arsenic material for comparing with any other sorbent material at the residing pH of the ZPC of the CuO of water particle; 2) arsenite and arsenate have suitable atomic size, so these atomic motions are in the CuO morphology of particles; And/or 3) in the pH of 7-9 scope, Cu2+ may cooperate with arsenite from CuO particle dissolved, itself so that adsorbed by the CuO particle.Described data declaration, CuO particle can be under different conditions be reduced to the arsenite in the water and arsenate and be significantly less than the desired pollutent limit of people's tap water, 10 micrograms per litre.
Method of the present invention is rapidly, and does not require pH regulator.The common ion of in the water other does not influence removing of arsenic material.In addition, described method is simple, effective and cheap.In addition, described method does not produce deleterious byproduct.Method of the present invention can solve serious health and environmental problem that under-developed country and developed country face by the quality of the tap water that improves under-developed country and developed country and rely on.
Conclusion:
1. arsenate and arsenite have shown the strong affinity to CuO in the water.
2. when using 0.5 gram CuO, arsenate and arsenite can be removed from water under high-sulfate concentration.
3.CuO removed arsenate and arsenite effectively from the natural water spike.
4. can use CuO to come from the water of tap water and/or pollution, to remove the arsenic material effectively, and need not to regulate natural pH.
Be used for removing the system of arsenite and/or arsenate, as shown in Figure 2, comprise the oxidation stage that is used for the arsenic of liquid is converted into As3 and/or As5 from tap water.The cupric oxide exposure chamber is configured in the downstream of oxidation stage, is used to hold cupric oxide and is used for mixed oxidization copper and the liquid that comprises As3 and/or As5.Strainer is configured in the downstream of exposure chamber, is used for removing one or more arsenic title complexs from liquid.Described system can also comprise activated carbon chamber, is used to hold filtered liquid and is used to receive the mixed bed ion exchange medium of the liquid of activated carbon filtration.
Be used for removing from water the processing and the filter system of arsenite and/or arsenate, as shown in Figure 3, comprise the cupric oxide contact segment, it is used for cupric oxide and the reaction that is included in the arsenic of current, and this reaction produces arsenite and/or arsenate.Activated charcoal filter is configured in the downstream of cupric oxide contact segment.Mixed bed ion exchange section downstream that is configured in activated charcoal filter, and cupric oxide contact segment wherein, activated charcoal filter and mixed bed ion exchange section are placed on and are suitable for being connected in the housing at water source.The housing of processing and filter system is fully compact, so that described system can be fixed in the outlet of family's water tap.
Below explain and describe in detail the illustration of exemplary illustration of the present invention and preferred embodiment in the accompanying drawings, instructed various corrections and alternative embodiment.Though the present invention is showed, describe and explanation, what those skilled in the art should understand that is, do not deviating under practicalness of the present invention and the scope, can make the equivalence change to form and details, and except being got rid of by prior art, scope of the present invention is only limited by claim.In addition, the present invention disclosed herein can compatibly implement under the situation that does not have specific factor disclosed herein to exist.

Claims (17)

1. method that is used for removing arsenite and arsenate from liquid, described method comprises:
Make described liquid and cupric oxide (CuO) one scheduled time of particle reaction; With
The liquid of filtering reaction.
2. the process of claim 1 wherein that described liquid has about 6.0 pH.
3. the process of claim 1 wherein that described liquid has the pH between about 7.5 to about 8.5.
4. the process of claim 1 wherein of the method production of CuO particle by may further comprise the steps:
Make the reaction of sodium hydroxide and cupric chloride;
Form copper hydroxide;
Copper hydroxide is at room temperature placed a scheduled time;
Be precipitated as cupric oxide; With
With CuO particulate filter, drying with grind to form fine powder.
5. the process of claim 1 wherein that filtered liquid has the arsenic concentration less than about 10 micrograms per litre.
6. the process of claim 1 wherein that the amount of CuO particle is about 0.5 gram.
7. system that is used for removing arsenite and/or arsenate from liquid, described system comprises:
Be used for arsenic being converted into As at liquid 3And/or As 5Oxidation state;
The cupric oxide exposure chamber, the downstream that it is configured in oxidation state is used to hold cupric oxide and is used for mixed oxidization copper and the liquid that comprises As3 and/or As5; With
Strainer, the downstream that it is configured in the exposure chamber is used for removing one or more arsenic title complexs from liquid.
8. the system of claim 7, wherein said liquid is tap water.
9. the system of claim 8, it also comprises:
The activated carbon chamber that is used for the liquid of receiving filtration.
10. the system of claim 9, it also comprises:
Be used to receive the mixed bed ion exchange medium of the liquid of activated carbon filtration.
11. the system of claim 7, wherein glassware for drinking water has about 6.0 pH.
12. the system of claim 7, wherein glassware for drinking water has the pH between about 7.5 to about 8.5.
13. the system of claim 7, the wherein method production of CuO particle by may further comprise the steps:
Make the reaction of sodium hydroxide and cupric chloride;
Form copper hydroxide;
Copper hydroxide was at room temperature placed about one day;
Be precipitated as cupric oxide; With
With CuO particulate filter, drying with grind to form fine powder.
14. the system of claim 7 wherein is filled into mixing water and has less than about 10 micrograms per litre arsenic concentrations.
15. the system of claim 7, wherein the amount of CuO particle is about 0.5 gram.
16. a processing and a filter system that is used for removing from water arsenite and/or arsenate, it comprises:
The cupric oxide contact segment, it is used for cupric oxide and the reaction that is included in the arsenic of current, and this reaction produces arsenite and/or arsenate;
Activated charcoal filter, it is configured in the downstream of cupric oxide contact segment; With
Mixed bed ion exchange section, it is configured in the downstream of activated charcoal filter, and cupric oxide contact segment wherein, and activated charcoal filter and mixed bed ion exchange section are placed on and are suitable for being connected in the housing at water source.
17. the processing of claim 16 and filter system, wherein said housing are fully compact, make described system can be fixed in the outlet of family's water tap.
CNA2004800342747A 2003-09-19 2004-09-17 System and method for removing arsenite and arsenate from water Pending CN1882507A (en)

Applications Claiming Priority (2)

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US50432903P 2003-09-19 2003-09-19
US60/504,329 2003-09-19

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EP (1) EP1678086A4 (en)
JP (1) JP2007505736A (en)
CN (1) CN1882507A (en)
AU (1) AU2004274472B2 (en)
BR (1) BRPI0414173A (en)
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